The reactivity of the dinuclear cyclopalladated complexes derived from secondary benzylamines, [Pd2{(C,N)eC6H4CH2NH(R)}2(m-X)2] [X ¼ Br, R ¼ t-Bu (1a); X ¼ Cl, R ¼ t-Bu (1b); X ¼ Cl, R ¼ Et (1c)] is reported. 1a reacted with dimethyl acetylenedicarboxylate (DMAD) to yield the mono-inserted complex [Pd2{(C,N)eC(CO2Me)]C(CO2Me)C6H4CH2NH(t-Bu)}2(m-Br)2] (2a). 1a, 1b and 1c reacted with (R0) C^C(R0) (R0¼ CO2Me, Ph) to give [Pd{(C,N) C(R0)]C(R0)C(R0)]C(R0)C6H4CH2NH(R)}X] [X ¼ Br, R ¼ t-Bu, R0¼ CO2Me (3a); X ¼ Cl, R ¼ t-Bu, R0¼ Ph (2b); X ¼ Cl, R ¼ Et, R0¼ Ph (2c)] through a double insertion of the alkyne into the PdeC s bond. 2c also reacts with Ag(CF3SO3) and pyridine to give mononuclear cationic complex [Pd{(C,N)eC(Ph)]C(Ph)C(Ph)]C(Ph)}C6H4CH2NH(Et)(py)]CF3SO3 (3c). The crystal structures of di-inserted complexes 2b, 2c and 3c have been determined by X-ray diffraction studies. Their molecular structures showed that the conformation of the C]C double bonds within the buta- dienyl group attached to the aromatic ring was transecis. Density functional theory (DFT) calculations also indicated that this arrangement is more stable than other possible conformations.

Structural and theoretical studies of mono and di-insertion of symmetric alkynes into the Pd–C σ bond of cyclopalladated secondary (tert-butyl and ethyl) benzylamines / Kazem, Karami; Mahboubeh Hosseini, Kharat; Rizzoli, Corrado; Hossein, Tavakol; Janusz, Lipkowski. - In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. - ISSN 0022-328X. - 752:(2014), pp. 152-160. [10.1016/j.jorganchem.2013.11.030]

Structural and theoretical studies of mono and di-insertion of symmetric alkynes into the Pd–C σ bond of cyclopalladated secondary (tert-butyl and ethyl) benzylamines

RIZZOLI, Corrado;
2014

Abstract

The reactivity of the dinuclear cyclopalladated complexes derived from secondary benzylamines, [Pd2{(C,N)eC6H4CH2NH(R)}2(m-X)2] [X ¼ Br, R ¼ t-Bu (1a); X ¼ Cl, R ¼ t-Bu (1b); X ¼ Cl, R ¼ Et (1c)] is reported. 1a reacted with dimethyl acetylenedicarboxylate (DMAD) to yield the mono-inserted complex [Pd2{(C,N)eC(CO2Me)]C(CO2Me)C6H4CH2NH(t-Bu)}2(m-Br)2] (2a). 1a, 1b and 1c reacted with (R0) C^C(R0) (R0¼ CO2Me, Ph) to give [Pd{(C,N) C(R0)]C(R0)C(R0)]C(R0)C6H4CH2NH(R)}X] [X ¼ Br, R ¼ t-Bu, R0¼ CO2Me (3a); X ¼ Cl, R ¼ t-Bu, R0¼ Ph (2b); X ¼ Cl, R ¼ Et, R0¼ Ph (2c)] through a double insertion of the alkyne into the PdeC s bond. 2c also reacts with Ag(CF3SO3) and pyridine to give mononuclear cationic complex [Pd{(C,N)eC(Ph)]C(Ph)C(Ph)]C(Ph)}C6H4CH2NH(Et)(py)]CF3SO3 (3c). The crystal structures of di-inserted complexes 2b, 2c and 3c have been determined by X-ray diffraction studies. Their molecular structures showed that the conformation of the C]C double bonds within the buta- dienyl group attached to the aromatic ring was transecis. Density functional theory (DFT) calculations also indicated that this arrangement is more stable than other possible conformations.
Structural and theoretical studies of mono and di-insertion of symmetric alkynes into the Pd–C σ bond of cyclopalladated secondary (tert-butyl and ethyl) benzylamines / Kazem, Karami; Mahboubeh Hosseini, Kharat; Rizzoli, Corrado; Hossein, Tavakol; Janusz, Lipkowski. - In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. - ISSN 0022-328X. - 752:(2014), pp. 152-160. [10.1016/j.jorganchem.2013.11.030]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2695083
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